Printing of textile fibers



' sulfoxylate and the like.

Patented Jan. 30, 1934 v PRINTING OF TEXTILE FIBERS- Sebastian- Gassnerand Herman Berthold, Leverkusen-on-the-Rhine, Germany, assign'ors toGeneral Aniline Works, Inc.,. New York, N. Y', a corporation of DelawareNo Drawing. Application May 19,- 1930, Serial No. 453,855, and inGermany May 29, 1929 27 Claims.

The present invention relates to improvements in the printing of cottonwith vat or sulfur dyestuffs.

In accordance with the invention cotton is printed according to anydesired method with printing pastes of vat or sulfur dyestuffscontaining besides the different ingredients, known for the preparationof such printing .pastes, an alkali metal salt of an unsubstitutedsulfonic or carboxylic 'acid of the benzene or naphthalene series or, ahydrogenation product thereof, or a benzene or naphthalene sulfonic acidsubstituted by alkyl groups or dialkylamino groups, or a benzene ornaphthalene carboxylic acid, substituted by alkyl-, hydroXy-, ordialkylamino groups.

It may be mentioned that the term printing pastes is intended to includeall kinds of pastes usually applied for cotton printing purposes, suchpastes for example as are obtainable by mixing vat dyestuffs withthickenings, water, glycerine or another similar water soluble alcohol,potassium carbonate, sodium carbonate, sodium formaldehyde sulfoxylate,sodium hydrosulfite or a mixture of the latter with sodium formaldehydeThe alkali metal salts of the sulfonic or carboxylic acids abovespecified may be added to the printing pastes at any stage of thepreparation of the same. The printing of.c otton with said printingpastes may be performed in the usual manner, for example, with the aidof a printing engine, whereupon the printings are dried to a certainextent, steamed with wet steam (e. g. in a Mather-Flatt) and developed'by oxidation, e. g., with an aqueous solution of an alkali metalbichromate and acetic acid, rinsed and soaped while boiling. It willalso be possible to use the pastes containing the sulfonic or carboxylicacids above specified in sloppadding processes, and it may be mentionedthat the best results are generally obtained when working with pasteswhich are reduced only on the fiber while steaming, which pastesgenerally do not contain hydrosulfites, but,- e. g., sodium formaldehydesulfoxylate as the reducing agent.

Numerous advantages result from the presence of the alkali metal saltsmentioned in the printing of cotton. In the first place it is possiblein this manner to obtain concentrated dyestuff pastes, which do notsettle or separate even on prolonged storing; in the second place it isfrequently possible to obtain dyestufi powders of a high degree ofdryness, which can be worked up immediately to very uniform printingpastes; thirdly, the addition of the alkali metal salts described aboveproduces in most cases a considerable strengthening of the printingsobtainable, which strengthening amounts in some cases to 40% and whichby far exceeds the action of sodium benzylaniline sulfonate, or othersimilar salts which are known as additions to printing pastes.

As alkali metal salts of the kind above referred to may be mentioned byway of example: Alkali metal salts of benzoic acid, ortho-toluylic acid,salicylic acid, phthalic acid, benzene sulfonic acid, para-toluenesulfonic acid, naphthalene-alphaand beta-sulfonic acid, dialkylanilinesulfonic acids, such as sodium dimethylor diethyl-metanilate, sodiumdimethylsulfanilate, sodium dimethyl-2-toluidine-4-sulfonate,furthermore, the sodium salt of cyclohexane carboxylic acid, .sodiumtetrahydronaphthalenebeta-sulfonate and so on. One or more of such saltsmay be added to the dyestuff preparations with a good effect.

The following examples will illustrate our in-' vention withoutrestricting it thereto:

Example 1 A. 20 parts by weight of '6.6'dichlor0-4.4'-di- 1methylbisthio naphthene indigo (in form of an aqueous paste) 15 parts byweight of the sodium salt of dimethylmetanilic acid 40 parts by weightof glycerine are evaporated in a plain pan until the paste has adyestuff content of 18%. The dyestuff preparation thus obtainable is ofpermanent durability,

does not settle as the aqueous paste, neither B. 10 parts by weight ofthe dyestuff preparations thus obtainable are mixed with 10 parts byweight of water and 80 parts by weight of a thickening containing inparts by weight 6 parts by weight of wheat starch 6 parts by weight ofBritish gum powder 16 parts by weight of gum 1:1 17 parts by weight oftragacanth 65:1000 10' parts by weight of glycerine 15 parts by weightof potassium carbonate 15 parts by weight of sodium formaldehydesulfoxylate and 15 parts by weight of water.

The printing pastes thus obtainable are used for printing purposes inthe ordinary manner. The printings are steamed whilst moist, developedwith potassium chromate-acetic acid and soaped while boiling. Theprintings produced in this manner on cotton are considerably morepowerful than those obtainable by the same directions but without theaddition of the alkali metal salts mentioned.

C. 20 parts by weight of the dyestufi preparations according to A. v10parts by weight of glycerine 2 parts by weight of sodium-benzylanilinesulfonate 15 parts by weight of potassium carbonate 12 parts by weightof sodium formaldehyde sulfoxylate 41 parts by weight of a thickeningcontaining in 100 parts by weight 35 parts by weight of British gumpowder 13 parts by weight of wheat stare 2 parts by weight sodiumbenzylaniline sulfonate 50 parts by weight water are used for printingin the same manner as under B.

Example 2 20 parts by weight of the finely divided dyestufi, obtainablein accordance with example 1 of British Patent No. 15,60'7/07 fromnaphtho-oxythiophen-carboxylic acid, in form of an aqueous paste 15parts by weight of sodium benzene sulfonate and 40 parts by weight ofglycerine are evaporated on the water bath with stirring until a pasteof 20% dyestufi content is obtained. The dyestufi preparation thusobtainable does not dry up and can be worked up immediately by thecustomary processes to printing pastes,

which on printing, for example, according to the process mentioned inExample 1, 3., yield more powerful printings than are obtainable withoutthe addition of sodium benzene sulfonate.

Example 3 3 parts by weight of a 60% dyestufi powder obtainable bydrying parts by weight of a 10.33% paste of the d'yestufi obtained inaccordance with Example 1 of'U. S. Patent No. 1,667,848, in the presenceof 2 parts by weight of calcined sodium carbonate and parts by weight ofthe sodium salt of dimethyl-metanilic acid in an enamelled drying dishon the water bath or on a roller dryer, heated by means of steam at 1/q--2 atmospheres pressure or by some other means, are mixed forprinting purposes with parts by weight of water and parts by weight of athickening as described in Example 1, B. The printings obtainable withthis paste in the usual manner are without stippling, they are fixedbetter and show a strengthening of shade compared with theprinting'obtainable according to the same method but without theaddition of the sodium salt of dimethylmetanilic acid.

Example 4 3 parts by weight of a 60% dyestuff powder, obtainable bydrying 484 parts by weight of an aqueous paste of the dyestufi specifiedin Example 1, together with parts by weight of the sodium salt ofdimethyl-metanilic acid and 2 parts by weight of sodium carbonate in themanner described in Example 3, are used for printing purposes asdescribed in Example 3. The printings on cotton even in printingprocesses without previous reduction are' considerably stronger thantheprintings obtainable from a normal aqueous paste of the same dyestuffmaterial without the addition of the sodium salt of dimethylmetanilicacid.

Example 5 v 30 parts by weight of the dyestufi of Example 1 in form ofan aqueous paste 19 parts by weight of the sodium salt ofdimethylmetanilic acid 0.5 parts by weight of sodium carbonate and 0.5parts by weight of sodium isobutylnaphthalenesulfonate (as' wettingagent) are evaporated to dryness in the manner described in Example 3.The powder is finely ground and sieved and can be used without furthertreatment for printing in the manner described in Example 3.

The sodium salt of dimethylmetanilic acid can also be replaced by thesodium salt of dimethyl- 2-toluidine-4-sulfonic acid.

Example 6 30 parts by weight of the dyestuff specified in Example 1,- inform of an aqueous paste 18 parts by weight of the sodium salt oftetra-- hydro -naphthalene beta sulfonic acid and 2 parts by weight ofsodiumcarbonate are worked up to a dry dyestufi preparation, asdescribed in Example 3 and display the same advantages in printing asdescribed in the preceding examples.

Example 7 30 parts by weight of3.3'-dichloro-N-dihydro-1.2-2'.1-anthraquinone-azine (in the form of anaqueous paste) 18 parts by weight of the sodium salt of Example 8 Whenthe dyestufi specified in Example 1 is replaced by flavanthrone andsodium benzene sulfonate is used instead of sodium dimethylmetanilate, apreparation likewise yielding stronger printings is obtained.

Example 9 tion likewise yielding stronger printings than a normalaqueous paste of the same dyestuff without the addition of. sodiumbenzene sulfonate, is obtained.

Example 10 In Example 1 the dyestuff can be replaced bydimethoxy-dibenzanthrone (Color Index page 265 No. 1101) and as theaddition sodium salicylate or sodium dimethylmetanilic acid can be used,in which case dyestufi preparations valuable in cotton printing arelikewise obtained.

Example 11 When the dyestuff specified in Example 9 is replaced by thatof the German Patent No. 242,621, a preparation likewise yieldingstronger printings is obtained.

Example 12 From the dyestuff obtainable according to Example 3 (firstdyestufi) of British Patent No.

201,786, glycerine, and the sodium salt of diethylmetanilic acid or thesodium salt of ortho- -toluylic acid, dyestuif preparations can beproduced in accordance with Examples 1 or 2, said vdyestuif preparationsalso yielding especially strong printings.

Example 13 From the dyestufi known in the literature (Scholl, Berichteder deutschen Chemischen Gesellsehaft Vol. 43, page 349) as pyranthrone,

in combination with the sodium salt of naphthalene-beta-sulfonic acid ordimethylmetanilic acid or dimethyl-2-toluidine-4-sulfonic acid valuableprintings are obtainable in accordance with the method described inExample 1.

Erample 14 The printing capacity of the dyestuif specified in Brit.Patent No. 23179/03 isimproved by the addition of, for example, thesodium salt of cyclohexane carboxylic acid, the sodium salt oftetrahydronaphthalene-beta-sulfonic acid, the sodium salt ofnaphthalene-alpha-or beta-sulionic acid.

Example 15 partsby weight of an aqueous paste containing 11% of6.6-diethoxy-2.2'-bis thionaphtheneindigo (Color Index No.

1217) v 40 parts by weight of crude glycerine 88% 1 15 Parts by weightof the sodium salt of bencontaining sodium benzene sulfonate.

with printing pastes comprising a vat dyestuil zene sulfonic acid.

I 3 Example 16 I 356. 5 parts by weight of an aqueouspaste containing11.2% of the dyestuif obtained from bromo-1-chloro-2.3 naphthisatin' and4 -methoxy-1-naphthol in accordance with the example of Brit. Patent No.289,154

parts by weight of glycerine and parts by weight of the sodium salt ofdi- 7 methylmetanilic acid are concentrated until the paste again showsa dyestuff content of 11.2%.

Example 1? parts by weight of 4.7-4'-7'-tetramethyl-5.5-dichlorobisthionaphthene indigo (in the form of an aqueous paste)parts by weight of crude glycerine .parts byweight of the sodium salt ofbenzene sulfonic acid are concentrated to a dyestuif content of 17%.

The dyestufi preparations obtainable in accordance with the lastexamples also display, when used for printing purposes after working upto printing pastes in any desired manner, the valuable propertiesalready described.

We claim: I 1. Process which comprises printing cotton with a printingpaste comprising a vat dyestuff and an alkali metal salt of a compoundof the group consisting of unsubstituted sulfonic and carboxylic acidsof the benzene and naphthalene series, hydrogenation products thereof,benzene and naphthalene sulfonic acids substituted by alkyl groups ordialkylamino groups, and benzene or naphthalene carboxylic acidssubstituted by a1kyl;, hydroxyor dialkylamino groups.

2. Process which comprises printing cotton and an alkali metal salt ofan unsubstituted benzeneor naphthalene-sulfonic acid.

3. Process which comprises printing cotton with printing pastescomprising a vat dyestuff and an alkali metal salt of a dialkylaminobenzene sulfonic acid.

4. Process which comprises printing cotton with printing pastescomprising a vat dyestufi, and an alkali metal salt of a di'methylaminoben- 5. Process which comprises printing cotton with printing pastescomprising a vat 'dyestuif and an alkali metal salt of benzene sulfonicacid.

6. Process which comprises printing cotton with printing pastes derivedfrom vat dyestuffs, said pastes comprising an alkali metal salt oftetrahydronaphthalene sulfonic acid.

' -'7. Vat dyestufi preparations consisting of a vatdyestuff, water,glycerine and an alkali metal salt of a compound of the group consistingof unsubstituted sulfonic and carboxylic acids -of the benzene andnaphthalene series, hydrogenation products thereof, benzene andnaphthalene sulfonic acids substituted by alkyl groups or dialkylaminogroups, and benzene or naphthalene salt of an unsubstituted benzene ornaphthalene sulfonic acid.

9. Vat dyestuff preparations consisting of a vat dyestufi, water,glycerine and an alkali metal salt of a dialkylamino benzene sulfonicacid.

- 10. Vat dyestufi preparations consisting of a vat dyestufi', water,glycerine and an alkali metal salt of a dimethylamino benzene sulfonicacid.

'11. Vat dyestufi preparations consisting of avat dyestufi, water,glycerine and an alkali metal salt of benzene sulfonic acid.

12. Vat dyestuff preparations consisting of a.

vat dvestufi, water, glycerine and an alkali metal salt oftetrahydronaphthalene sulfonic acid.

13. Printing pastes suitable for printing cotton, which comprise a vatdyestuif, a; thickening and an alkali metal salt of a compound of thegroup consisting of sulfonic and carboxylic acids of the benzene andnaphthalene series, hydrogenation products thereof, benzene andnaphthalene sulfonic acids substituted by alkyl groups or dialkylaminogroups, and benzene and naphthalene carboxylic acids substituted byalkyl-, hydroxyor dialkylamino groups.

14. Printing pastes suitable for printing cotton, which comprise a vatdyestufi, a thickening and an alkali metal salt of anunsubstitutedbenzene or naphthalene sulfonic acid.

15. Printing pastes suitable for printing cotton, which comprise a vatdyestufl', a thickening and an alkali metal salt of a dialkylaminobenzene sulfonic acid.

16. Printing pastes suitable for printing cotton, which comprise a vatdyestuff, a thickenand an alkali metal salt of tetrahydronaphthalenesulfonic acid.

19. The process which comprises printing cotton with aprinting pastecomprising 6.6- dichloro-4.4'-dimethyl bisthionaphthene indigo, and analkali metal salt of a compound selected from the group consisting ofdimethylmetanilic acid, dimethylsulfanilic acid and salicyclic acid.

20. The process which comprises printing cotton with a printing pastecomprising the dyestufi cotton with a printing paste comprising 3.3-di-I chloro-N-dihydro-1.2.2.'.1-anthraquinone azine and an alkali metalsalt of 'tetrahydronaphthalene-beta-sulfonic acid.

22. A printing paste comprising 6.6'-dichloro 4.4dimethylbisthionaphthene indigo and an alkali metal salt of a compoundselected from the group consistingof dimethylmetanilic acid,dimethyl-sulfanilic acid and salicylic acid. I

23. A printing paste comprising the dyestufi obtainable fromnaphtho-oxythiophene carboxylic acid by oxidation with potassium ferriccyanide in caustic soda solution, and an alkali metal salt of benzenesulfonic acid.

24. A printing paste comprising 3.3'-dichloro-N-dihydro-1.2.2.'.1'-anthraquinone azine and an alkali metal salt oftetrahydronaphthalene-betasulfonic acid. I

25. A vat dyestuif preparation consisting of6.6'-dichloro-4.4'-dimethyl-bisthionaphthene indigo, water, glycerineand an alkali metal salt of a compound selected from the groupconsisting of dimethyl-metanilic acid, dimethylsulfanilic acid andsalicylic acid.

26. A vat dyestufi preparation consisting of the dyestuff obtainable byreacting upon naphthoxythiophene-carboxylic acid with potassium ferriccyanide in caustic soda solution, water, glycerine and an alkali metalsalt of benzene sulfonic acid.

27. A vat dyestufi preparation consisting of 4 3.3dichloro-N-dihydro-l.2.2'.1' -anthraquinone azine, water, glycerine, andan alkali metal salt of tetrahydronaphthalene-beta-sulfonic acid.

SEBASTIAN GASSNER. HERMANN BERTHOLD.

